ABSTRACT
A novel empirical potential has been developed to evaluate the thermodynamic stability of Ni(1-x)Fe(x)Cr2O4 spinels. The simulations confirm the hypothesis that the NiCr2O4-FeCr2O4 pseudo-binary has normal structure spinel up to 1000 K and stabilizes as a solid solution. However, the disordering energy (normal to inverse spinel) is found higher for FeCr2O4 than for NiCr2O4 spinel. The formation energies of tilt, twist, and random grain boundaries have been calculated in pure NiCr2O4 and FeCr2O4. The same behavior has been found for both spinels. Detail analysis of the grain boundaries structure shows that the cation coordination number is a key parameter for the stability of the grain boundaries. With this criterion, we evidenced that the structural and energetic differences are caused only by nickel and iron cations.
ABSTRACT
Ruthenium, a fission product arising from the reprocessing of spent uranium oxide (UOX) fuel, crystallizes in the form of acicular RuO(2) particles in high-level waste containment glass matrices. These particles are responsible for significant modifications in the physicochemical behavior of the glass in the liquid state, and their formation mechanisms are a subject of investigation. The chemical reactions responsible for the crystallization of RuO(2) particles with acicular or polyhedral shape in simplified radioactive waste containment glass are described. In situ high-temperature environmental scanning electron microscopy (ESEM) is used to follow changes in morphology and composition of the ruthenium compounds formed by reactions at high temperature between a simplified RuO(2)-NaNO(3) precursor and a sodium borosilicate glass (SiO(2)-B(2)O(3)-Na(2)O). The key parameter in the formation of acicular or polyhedral RuO(2) crystals is the chemistry of the ruthenium compound under oxidized conditions (Ru(IV), Ru(V)). The precipitation of needle-shaped RuO(2) crystals in the melt might be associated with the formation of an intermediate Ru compound (Na(3)Ru(V)O(4)) before dissolution in the melt, allowing Ru concentration gradients. The formation of polyhedral crystals is the result of the direct incorporation of RuO(2) crystals in the melt followed by an Ostwald ripening mechanism.
